The role of van der Waals and exchange interactions in high-pressure solid hydrogen

文献信息

发布日期 2017-08-02
DOI 10.1039/C7CP03729E
影响因子 3.676
作者

Graeme J. Ackland


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摘要

We investigate the van der Waals interactions in solid molecular hydrogen structures. We calculate enthalpy and the Gibbs free energy to obtain zero and finite temperature phase diagrams, respectively. We employ density functional theory (DFT) to calculate the electronic structure and density functional perturbation theory (DFPT) with van der Waals (vdW) functionals to obtain phonon spectra. We focus on the solid molecular C2/c, Cmca-12, P63/m, Cmca, and Pbcn structures within the pressure range of 200 < P < 450 GPa. We propose two structures of the C2/c and Pbcn for phase III which are stabilized within different pressure range above 200 GPa. We find that vdW functionals have a big effect on vibrations and finite-temperature phase stability, however, different vdW functionals have different effects. We conclude that, in addition to the vdW interaction, a correct treatment of the high charge gradient limit is essential. We show that the dependence of molecular bond-lengths on exchange–correlation also has a considerable influence on the calculated metallization pressure, introducing errors of up to 100 GPa.

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来源期刊

Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
CiteScore: 5.5
自引率: 10.3%
年发文量: 3036

Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.

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